Process for the selective hydrogenation of epoxyalkenes to epoxyalkanes

Abstract

Disclosed in a process for the homogeneous, catalytic hydrogenation of epoxyalkenes and epoxycyclo-alkenes, especially conjugated γ,δ-epoxyalkenes and epoxycycloalkenes, to the corresponding epoxyalkanes and epoxycycloalkanes using a solution of a complex rhodium catalyst whereby the olefinic unsaturation is hydrogenated without significant hydrogenolysis of the conjugated epoxy group.

I claim: 
     
       1. A catalyst solution comprising (A) an inert, organic solvent and (B) catalyst components dissolved in said solvent comprising (i) rhodium, (ii) an organophosphorus compound selected from trihydrocarbylphosphines and trihydrocarbylphosphites, and (iii) a poly-unsat-urated hydrocarbon selected from alkadienes, cycloalkadienes, alkatrienes and cycloalkatrienes; wherein   the ratio of moles of component (ii) to gram atoms of rhodium is about 3:1 to 50:1; and   the ratio of moles of component (iii) to gram atoms of rhodium is about 2:1 to 150:1.   
     
     
       2. A catalyst solution according to claim 1 comprising (A) an inert, organic solvent containing up to about 12 carbon atoms and (B) catalyst components dissolved in said solvent comprising (i) rhodium, (ii) a trihydrocarbylphosphine, (iii) a poly-unsaturated hydrocarbon selected from alkadienes and cycloalkadienes containing 4 to 10 carbon atoms, and (iv) a non-nucleophilic gegen ion; wherein   the ratio of moles of component (ii) to gram atoms of rhodium is about 3:1 to 50:1;   the ratio of moles of component (iii) to gram atoms of rhodium is about 2:1 to 150:1.   
     
     
       3. A catalyst solution according to claim 2 wherein the organic solvent is a ketone having 3 to 8 carbon atoms. 
     
     
       4. A catalyst solution comprising (A) an inert, organic solvent selected from ketones containing from 3 to 8 carbon atoms and (B) catalyst components dissolved in said solvent comprising (i) rhodium, (ii) a trihydro-carbylphosphine wherein each hydrocarbyl group contains up to about 12 carbon atoms, (iii) a poly-unsaturated hydrocarbon selected from alkadienes and cycloalkadienes containing 4 to 10 carbon atoms, and (iv) a non-nucleophilic gegen ion; wherein   the ratio of moles of component (ii) to gram atoms of rhodium is about 4:1 to 20:1; and   the ratio of moles of component (iii) to gram atoms of rhodium is about 5:1 to 10:1.   
     
     
       5. A catalyst solution according to claim 4 wherein (i) the concentration of rhodium in the catalyst solution is in the range of 100 to 2000 ppm, (ii) the trihydrocarbylphosphine is selected from triphenyl-phosphine, tricyclohexylphosphine and tribenzylphosphine, and (iii) the non-nucleophilic gegen ion is selected from hexafluorophosphate and boron compounds having the formula (R 5 ) 4  B -  M +  wherein R 5  is selected from fluorine, hydrogen, alkyl, aryl, or hetero aryl, and M is an alkali metal. 
     
     
       6. A catalyst solution comprising (A) an inert, organic solvent selected from ketones containing from 3 to 8 carbon atoms and (B) catalyst components dissolved in said solvent comprising (i) rhodium, (ii) a trihydrocarbylphosphine wherein each hydrocarbyl group contains up to about 12 carbon atoms, (iii) a polyunsaturated hydrocarbon selected from alkadienes and cycloalkadienes containing 4 to 10 carbon atoms, (iv) a non-nucleophilic gegen ion, and (v) iodide; wherein   the ratio of moles of component (ii) to gram atoms of rhodium is about 4:1 to 20:1;   the ratio of moles of component (iii) to gram atoms of rhodium is about 5:1 to 10:1 and   the ratio of gram atoms of iodide per gram atom of rhodium is about 0.25 to 5.0.   
     
     
       7. A catalyst solution according to claim 6 wherein (i) the concentration of rhodium in the catalyst solution is in the range of 100 to 2000 ppm, (ii) the trihydrocarbylphosphine is selected from triphenylphosphine, tricyclohexylphosphine and tribenzylphosphine, and (iii) the non-nucleophilic gegen ion is selected from hexafluorophosphate and boron compounds having the formula (R 5 ) 4  B -  M +  wherein R 5  is selected from fluorine, hydrogen, alkyl, aryl, or hetero aryl, and M is an alkali metal.